Chirality dependent inverse-melting and re-entrant gelation in α-cyclodextrin/1-phenylethylamine mixtures

Solutions of cyclohexakis-(1→4)-α-D-glucopyranosyl, α-cyclodextrin, αCD, in R-(+)-1-phenylethylamine, αCD/R-PEA, and S-(−)-1-phenylethylamine, αCD/S-PEA, display abnormal phase transitions that strongly depend on supramolecular diastereomeric interactions. While αCD/R-PEA mixtures show one sol–gel inverse-melting phase transition, αCD/S-PEA mixtures show temperature dependent gel–sol–gel re-entrant behavior. NMR, Raman spectroscopy, microscopy and X-ray scattering measurements reveal that hydrogen bond weakening in solution, as well as changes in crystal composition are responsible for entropy increase and gel formation upon heating.